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Fishery Leaflet 174

'j"W'ashington 25, D. C. ---._-------, Reissued January 1950 --- -~-

ST!:?SAM POLLUTION HAZARDS OF ;IVQOD PULP LILt EFFtUET-TTS

By B. A. Westfall, Ph.n., Formerly Aquatic Physiologist, Branch of Fishery Biology

Introduction

In the United states the production of wood I)ulp which st~rted with a few ground-pulp mills in the northern forest areas has grown into one of the Nation's maj or chemical Ll1dustries. An increasing demand for C'aper and wood-pulp products resulted in the development of several chemical processes which gave great impetus to wood pulp production. Although these chemical operations, particularly the sulfite process, i:lcrease the efficiency and the output of the pulp industry, they have broUGht with them wastes which present difficult disposal problems. Followin,:: the preced.ent set by other industries, thes'3 wastes in many cases r:a '"e been flumen into streams and se;-ious pollution condi tions have resul ted.

With the development by industrial chemistry of commercial rayon and cellophane plants a still greateriemand f01· wood pulp :us be',m created in the past few years, so that the ')ul} industry is now cxranlinr: into nev{ 10c'3.tions. These ne'll pul? mills are econorr,ically ver:,T r1csirr.l bl c , but they ha.ve magnified the str ',.am pollution probler:i because of the; in­creasingly larger volumes of chemical efflu'3nts for which the :)Ulp industr:' must find an outlet.

As ther ,':! are s cv 3ral ty~l(~S of pollution hazardspr8sonted tv the pulp mill Hffluantsand as some of tho ~ff~cts of these waste s are cumulative rather than im.r.1ediate, the detrir.1Gntal "iction of t :lose pulp effluents on fish and other aquatic l~fe cam-l()t be measured by any si.ngle standard. Consequently in this memorandum the d :- tails of the hazards to fish life produced by the sev.:: ral kinds of waste s from pul::> r.:ills are reviewed individually.

In presenting the major pollution hazards which may be expected when wood pulp effluents are introduc~d into streams ani oth8r waters, average conditions are discussed. Industrial processes are not fixed entiti8s, howev'; r, arid the ' details of individual plant procedu, '3s not

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only vary but ar c changed fr'3qusntly in the 'interest of efficiency and e conomy. Cons'equently specific applications of the se statements of haz a rds can only be made when' 'supporting data on both local stream condi 1;'ions and the op ~ rations of the concern in question have been con sidc:rei, as wood pulp effluents are not uniform in composition, concentration, or in degree of de~rimental action~

!"ST~IG'i)S OFN00-:-J PULP ':lEODUCTION AND T[~'EIR SFFLUENTS

Four processes and various combinations of the se are userl cur­r'~;1tly in t he production of commercial wood pulp, and the effluents di f f e r accordingly .

Grouni ~'rooi Pulp

Ground wood pul p is r.mdo by pressing lObS against re'Volving grindstones, a streaIJ1 of '.'la.terwashin[ away ite pulp and depositing it on screens.' The wa ste water from this process carries some pulp an d wood dust which passe s the s c r "Hns and va ryi.ng amotL'1ts of the solu­ble 8xtracti ves from t he woo:': d epending upon the quantity 9.ll(1 temp6ra~ ' t u r e of tho ,va t e r use d, t he kind of 'Nood being grmmd. and the previous tr0a t wen t o f the logs, i. e. wh ethor they Wdre steamed, soaked or dri ~d ' be fore grinning. Even though this m3thod usually includes no extensi va 'ldditionof chemicals, ' the a queous solution carrying extractives from such fin ely iivide n woods, espe cially of ' pine, is often somewhat toxic t o th e Rquatic organisms coming in conta ct with it.

Soda Pulp

Soda pulp is pro3.ucad by digesting wood chips in a strong snlution of caustic soda , the pro ce ss baing expedite d by the use of he at and ? r ~ ssure . The pulp is recovere d on scresni from a strongly alkaline brovmish liquor of h igh s pecific gravity containi!1.g a large number of org9.nic cornpounds dori ve d from the disinte gr9t e d wood. The soda liquor "rhi ch 8,lw'1.Ys conta ins SOID e unr '3cover6d pulp is the refore a m.ixture of 'r ':~ r :·r v;ub.bl e c omp osition de p0ndingupon the kir~d of wood I1sw<311 as ~ p on t he dura tion of t~e digestion p eri6d, the strength of the alkali cmd ot iv.:: r f 'lc tors. As 11 18. rge pe rcentage of the soda :liquor 'is recov0red a t t ho plant (~t l east 95 pe rc0nt, Wi~ham, 1942) the ,effluents from soda pulp mills :t re chiefly alka line wash w'1.t <J rs carryin.g varying amou..>'lts of diluted sod~ liquor contqining extra ctives from the wood together *ith such pu lp a s is lost through the scr~ 6ns.

Sulfite Pulps

Sulfite: pulps e re obta ine d by the action of lime and magne.si a bisulfites on wood chips in thepros ence of e xcoss sulfur dioxide in soluti on, a idGd by h e<.1. t and pr0ssure . After r e cov <; ring the pulp on scr,:e ns a strongly acid fluid rcmuins which includes in its !s.rge and v'l riabl e list of components th8 disintegra tion products of th e wood

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many of which are sulfonated, several typns of sulfur compounds, · some pulp, and '1. In.rgo amount of extractives. Although some of the sulfite liquor is reolaimed or othcrwis] used at present, the c::ffluents from sulfite mills include the sulfite liquor, " various wn.sh wate rs used. in removing tho sulfite liquor from tho pulp, a large amount of wood ex­tre.ctives in solution and always some pulp.

Sulfate Pulps

Sulfate pulps used in the m~nufacture of the Kraft papers are the products of a process which combines some of the active agents from both the soda 8.nd sulfite proeGsses, as incmnpletely reduced sodium sulfate (salt cake), i. e., a mixtur~ of sodium sulfate, sodium sulfide, sodium carbonate D.nd sodium hydroxide toget1::ter vfi th variable quanti ties of the complex sulf~tes and sulfites, is used as the digestant for the wood chips. After :,eIToval of the Su:f'lte pulp a wast e fluid called "'black liquor" r ,3mfl.ir.s which is 2.1b\lino in re ,lCtion and C D rries a vnriety of compounds soce of t.hem sulfon"',-1:;8:i, rasulting from the dis­integration of t~ld wood in t:-V3 digest::or. Since Kr3.ft pulps r.>reusupl1y not cooked out us cornp1 8tely as sulf~ta pulps, the or~cnic content of the black liq110r is genl.::'l"'l.lly !lot ').s hiGh n.s th?,t of the sulfite liq'Jor.

In ecr.trast, to t1:"'!0 s1.l1fi t8 pron~ss, the waste fr.om the sulfr .. te ~roce ss dO C0 not contain nc';.r1y :.. S 19.rG::: ~. p.:rc~' nt~~ ge of org8.nic Jii"t '3rial cmd ch'3micn.ls, for the r3cov:r;T of h":'1.t sYlE'rgy nnd chemicals from the sp'::;nt li..quor by 8vapor'l.tion '1.1':d bU!'Yl1''lg is on ~ of t t0 outstanding :'c~,t.ur "'; s

of ths sulf~t0 m0thod. In f~ct With'l.m (1~42) ~ f Jrs to v~rious typ ns of r '~: cO'J ~ry systems l,vhich S9.'TeJ 95 p,j rcont of the chemic9.J.s or in some C'l.ses e1;cn mar ::: . Sut t; rmeistor (1941) cO!lsid'2 rs r!. J.os~'j of 40 pounds of s'llt c ,lke p::r ton of fiber )Jrorluce r> an i '·l di~ ·} tj on of sU~:H rior Op31·n.ti~g con­ditions. Altho'.l.6; tl'H3 p3rccrLtag',; of chemicals <.m i extrf.'.ctives lo st is r e l~tively small. th~ load entering the stra'lm vi~ the waste from the plfJ.nt, v/her. hundrods of tares of pulp ,-tr c produce d d:~ily, cnn. be quite b .rgc indc,ed.

EF'FECTS OF ?ULP I;ITLL EJi'FLU?:.JTS Or: AQUATIC LIFE

Tho effluents from all of th ':; ),roe ') ss(Js 1;;!lUrr,.3l"o.t'3d are da::1nging to aquatic life becFl.us~ of the~JUlp fib'3:!"'s whicp are lost, the oxygen demand of tho unst.J.ble COJT:?ouJ'd s libsr.:~ted from the wood or pro1uced :luring th (;) op0re.tions, and the SD'::7cii'ic toxic action of v.':1. rio1.lS substo'nces.

Blanketing Effect of Wood Pulp

Tho introduction of wood pulp irltO strc'lffiS awl. oth8r waters, rm,i all pulp mills lose sone pulp, is ~,Hng·?rOus to v.qw'ltic life largely bccD.use cellulose fibers do not disint'~': gr"te rrlpi11y in tho '!later fmd thcrI:Jfore accumulate, cov~·;ring subm:rgGd obj.:: cts and blanketing the str'Jam floor.' These b.y .~rs of ·wood. pulp cl.ecraas6 the productivity of the stream by smoth-:;ring out l'lrge numbdrs of food orgc:misms, by cover­ing spa1,rl!ning beis, oni by ha.rboriilg undEisir'1ble fungi [,ni b8.ct~ri8..

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Vr:.llin (l939) errpha r:;iz e d that fibt"n"s collect slim0 and Jetritus 'and .J c: s trov the bottom lifo on which fish sUbsist. As pulp fibers r ea.dily r:lo. t "lo~;m with silt ani sewag0, wood pulp also greatly incr'Y1ses th8 p ollut i on hlJ.za r ~ s fro~ the s e sourc o s.

Ex p erim: n t'll work has shown that healthy adult fish of several . s V3c i e s may 3urv iv8 in susp ensions of woor! pulp for 20 de.ys or more without anp'l r cnt da~a ge if the gill action of the fish is goa1. These t e s t s h '1ve been offc:re d r e pe r:. t e dly as showing that ' .. ,rood pulp is not in j ,.lri oHS to fish life . It has a lso been establishe d, however, that yOU ".b fis h often be cone hop ':~ lessly eYlb.ngL~ d. in mats of woo d pulp, and t h r, t the g ills of both young 1l;! ·1. 1). '~.1.l1t fish ~lT"e spo o1ily clogge-1 with wo od Dulp fibe-r if the fish is incfln8.ci t l'.tGJ. evon for a short time or ',vea ken e d.

It ha s ~ lso b e e n pointed out thnt wood pulp is r ~lJ.ctily carried <iway b~r current a ction h rap i'l strer:UT!S. This is true, but U. S. Fish an I '~J'i1 dlife Service fidd pRrti e s working in Muine and othe r parts of t he country fOUl~ d tha t wood pul p , a l though v e ry large ly washe d away from t he iITU],.:; ,ji'lt,,, vic in ity of flu!Tlo S ente ring streRms wi th strong currents, W9- S deposite d in sl a ck ,!;,." t :~ rs SOl!'wti;ne s 15 to 20 miles downstream from t k poin t of entrano e . In tn.:; 8 8 quie ter portions of the rivers not only vms the str08 m floor c ov c:T 'J,l with pulp fi b o r but ne a r the coa st whe re tLial "lo t i on an J bra ckish wa t e r ~1. · t :l. eJ f D.ctors W'hich complicated the stream 'flow l :t;l(' rs of de nse pulp suspE:nsion s fiU e ·] the pools an '1 lower portion of the s t r :<'l.ffi be] f or a ve rtica l 1ista nce. of 3 to 6 fe a t 8bove the river floor.

Both fi e l1 ani expe rimentf: l ·.1a t a show th'3. t in gene r a l, the rietri­m~' ~'J ta l '3 ff e cts of woo~ pu.l p on stream con1 i ti ons as 2. whole and therefore OYl. the p ro-1.ll ctivity of the str ea.m ha ve been unde1'- e stima tec1 chiefly be­C (~.U SJ t ht} fl..b e rs r1.0 not kill fvlult fish i mrne ii ':l t e ly. Forbmately wood 1') 'l l ~ is the S 'l.l e::J.ble p ro duct of the pulp mills and the pulp industry has r :;·:t lize i t h .. ero r mou s loss whic h it form3rly suffe: r eJ through the lID­

r , ~ c ln.i r.l~ ' ;' pul p in tho "·:;hitewate r". Less nul p is lost each yen.r but it shoull b u r Ui :cmb e r e i tha t owine; to the cumulative buil ,l-up of pulp (le­pos its '.'e r :,' small a mO\.mts of pulp if suppli e i contir;uously can ultim~te ly

;:; ro~uce serious h mag:e to fish l i fe in o.lmost a.ny stre"m.

Re;lu~tion of Jissolve l Ox;:rgen in str ·~ r.! m Wa t Gr

The ~iqui '1 portion s of pul p rr.ill e ffluonts ca rry v).rious unsto.ble .J.r:-.~ ill1oxiliz8 1 c ompounls {largely organic subs t a.nce s l eachel or chemically ~isso l v,: l fr o:: the 'NOO 1 :'urinr th ] r ro ! u ~tion of the pulp) having high

oxyge n 'lemands. Thos e substnnc<3 s r na lily remove the -lissolvei oxygen from t h<::' wa t 'J rs of st n ' l "s r o ce iving pulp ',v;:st e s so toot o. quntic life in strdarns thu s POllutE '1 I"':'1Y f ; u:~ e CO'Y1. 1itions r~llging from unf tlvor o.bl e to a·sphYxb.l as r i:: g 'l rJs the lissolv21 oxygen. 'This irr.portance of the oxyge!1. 1emanri is well known t o the ?G.p·J r in :ustry (Te chnical Association of the Pulp an:l. P9.p·e r I n lustr;r 1943) ':111 1 to G. quQtic biologists.

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Sev',irnl factor:=:: ,bt·:rl'1ine the ro?i -1ity of tr8 rc;~cti.on of tho::::e compounJs having high oxygen 'le,':'ian l with th~ ,:'is501 V8~ oxygen ir. th0 stream wat()r but analysE's T:'ale in M:~L~e an ; Vlisconsir. she\". thn.t s'llfit'l liquor as taken from the ligcstcrs of ""00 ~-p1l1p pl'lnts o~or'ltbg in the Sp states has [l,n aV':)r'lge ons- 'a~.r oxygen iema;''ll of 'lpp:-oxir:~", t'.:;l~r

1,500 parts flpr million, although 'TIuny slln.phs run I::u:;h hig:1("r (Ul) to 8,000 p.p.m.) an l others much lower. Using this gross 'lVCrag3 ";1'1h.18

of 1,500 p.p.m. for B one-~ay o~ygGn lem'ln~, it m~y be seen th~t sulfito liquor co111·1 ~ro~ucG ve.ry:is''..strous effects on fish life thro~lgh th,) r'3duction of the 1isso1'.'8 l oxygen if ?ourf; 1 into str ':; lTTl wate rs, sinC0 the a~~rage lisso17~': oxygen contsnt of str ;~ms supporting ~ish life in the Units 1 States liES bet~3cn 4 3n: 9 p.p.~. nnl ~ re~uction of the 'lissolv·o·l oxygan to 3 '9.p.m. ~)ro !uce'~ cO:l1itions ':'lot only 'mf:1'.·orabl'J but approaching the critical for rrany fishes. Actual tests an~ fiGli observ8.tions h9VEJ ShO""T1 the.t un 1er ovcr3.ge con ~i ti0ns 8. ·1il,.tion of sulfite liquor to 1: 200 i..n t!1e strenm is usuD. ll~/ suff:'ci r:nt to M: ']t the oxygen 'leman-l of this w'.'ste without lo,';-:;rirg th::: 'n .ss01,' .:;.'l oXYt:cm of th : ~

str0am to a crit~c~l point, proviic~ ~ ~equat8 mixinr is ~ssur81.

COrlparinr tl,e four t:r~)e$ of p'll;: efflu .' nts, s111fi te liquor usu'llly has the hi;;hest oxy;,:;en " "~;-:() n~. Sulf, ':;0 'JL:.~ .lr liC!.uor ~~n 1 t"n .~H:'11in8

soja liquor glf'erally h~3V ::; 1(;55 oxygen iecr ::t'l ·l t1i"-:1 sulfite liq11Or' n.n-1 c;round woo ~ ,!ulp effluer.t o.lthour;h somctir:' C' s h03.-"inC an o~yg~r. ~err ·.vi'

e qual to 10 ,?crcent of thnt of s'.llfit ,:; liq'.lor r:.",Y ru.". os 10· .... '1. ~~ 2' ? ' j'(~ r~ nt

or less in l'clativ() ox;rgen Jerrnn:. Th", pro~ortio;l:, t (', ly 10'N o-V::'C 'm 'l'.r-·::,' of groun:l. woo ·~ pulp W'.~, t e r is not sur~rising w:, -:; r ~ it is r<' s r-;c _,c '. t·~· , t :": chs.micals s.re userl in this proc ,,':ss. The Se COIT ;-" r:.tiv.-: 'l'1.l.UOS ',lthcl.l~h

gi vin[- so'ne ilea of tho r 01 <l. ti VG rrngni tu l0 of t:··: ox~r~Vl '\::".D.:1ds of tr. ,~

four major pulp efflu-:mts rr.ust bo use ': wi th cqution sincr,; so T::'lny v C1ri'J.­bIGS are involve~.

Toxic Effects of Dissolv',:: Substmces

The specific toxicities of the four ;ajor types of pul:; ;:;fflut::"ts '-~re consiLr'3 ,:t sep'?lrCltely bee"l.llse of ·1iffcrc:nces ir: r'_"'lctiOl: :tn " ch(,r.i­cal cor~posi tion.

InUscussing the lethal conccntmti'Jns of t:: 'i:' se efflU':nts the dilutions are ulvinys e:'=pre ss,:; ·l in tr) r:.~ s of th~ ur.;'lix (; ~. liqui \ ;'['·.st;:; 'lS

-1.rawn from the digester. As ho.s been pointe 1 o~t :-;,;pe'1te ny, hew ', v 'r, oven iigestcr liquors nr0 not co~~t~nt in C0~Fosition an I 3S s0v8r~1 ~t least of the lmown toxic components of thcs'" wastS's !u"e -J'oll1til E:' , throuf,r, IlE1r(ltion ti.nd han n ing of s').mp10 slrn\l/Yl lircctl~.r f:- ,):,\ the.' S :'1.1~; e lig .) s":er, it is possible to obtD.iri wiJe v:lrbti:.ns in th3 Q':'-:;"r'rnt toxi~:'t:r 0:' liquors frO::l one rUT: of puJ. p. Conscq'.lcntJ y, the av.J rc.[3 ""ell ~,k S gi ";,:;r. can oalv be used to esti:"'-c,te the 03XP':3Ct·]; r::~tgnit'.ll( . . ):' t ·Jxicity. It r.!ust be

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r(~T'lcc:berej, 3.1so, th>lt the oxygGn j,Jr..B.:ll cf 1;h·a "1":stP. r:n ~ it~ sPecific toxicity ".re in1E:~~n1ent v"ri~tbles. 07:~lrL;-, 1.e~,,; :: ~ C·:.",r,ot S') us.::1 as Iln in~8X of ']vcn ralr.tiv~; toxicity sinco sc.;:-e of t~v, :'!ost toxic compon ents of thps0 1.v.:;.stes .10 not rrot.lc~ 8.r.y ()xv0er: len',n '.

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GrmID 'l woo.} pulp waste. --Theiissol ved substances in grouncl wood pulp waste w·tl.ters vnry greatly wi,th the kin (l of woo:l, but since 'only vmter is used in the process an ~l the logs are peelei before grin 'ling, thes.J ·o fflu·:mts are usually low in specifically toxic substances, an c! if the pulp fiber hllzo.rds are elimimlte i by proper scr(Hming an1 the oxyg::m ,lenan l,S of these waste waters :::tre met bya ~equate dilution ground wooi pulD w!'J, t 'o rs present little in the way of pollution problems from toxic- co~stituent;. These st'l tements, however, ~lo not apply to the stc 0pings from bark nor the leachingsfrom logs which 'lre pre-treated with steiJ.p.: or boiling water. Some confusion h<"\s arisen concerning the tox i d ty of groun:l wooi pulp e ffluents because groun 1 wooi pulp mills P.:'li:-,.t8in subsiUary <livisions in their pl9.nts which use bark or which sp ecifically tr8~t some kinls of lo gs. ~aste s from these particular proce sses, which a re not of course ?ulp processes, are often very toxic to fish ani other aquatic life either alone or when mixe1 with run-off wat e rs fro:n the pulp grin ling.

Sulfite liquor.--Sulfite liquor is strongly aci1 ani if large quan­tities of the iige ster liquor be poured into the gtr8am, fish in tJ-:te im­me'hate vicinity of the outl e t Jr:ily be kill-:d by the hydrogen ion effect of this effluent before it is rl ilute ~i. awl buffered by the stream water. It is ·iifficultto sb.te wher0 the -:tominant effect of the aci 'ls in the sulfi t o liquor l eave off an -l the more spe cific ef fects of other substances i n this wa ste begin, but in concen tr ;~'. tion s more acLl than pH 6 acidity is [~t l eo. st a contributing factor tD the lethal action of sulfite liquor. If t;1i. S wa ste is noutra liz '3d , howov ,J r, it ~till retains its toxic properties s o tha t the containei aci :1 s are only one group of toxic ingro lients.

Ex~ori r.lents cD.rrieJ out by v~:::.ri ous observers an'l at U. S. Fish and Wi l ·n i f 'J' S0 rvice IB.bor 3. tories in r1.ic9.te that the IDl.:'..ximum c~ncentration of s'llfit8 liquor, i. e., full strength as drawn from the r1,igester, in which if t he lissolve -l oxygen is properly maintain e'l warm v;ater 'fish wills1).z:v:ivE f or 10 to 20 hys, is ba t v"oen l: 200 8,ni l: 500. Trout m lother col~-wat 3 r

fish un ',er tho. S3.J7l8 con,litions succumb in c. fewiays, howtJver, to a conc.en­tr' :ti on of 1 :1,000 . The se figures give the gene::"al range of riilution re- . q'lir .?~ if ir.1Trle"l.i~ te injury to fish f c. un;;, is to b o 3.voile1. '.

It has been note-i rep0'1.tr,=J'lly, hm'lGver, thnt .both the fish fauna iln.,t tt f oc .~ or gnn isms gr o. :~ually (k cline in streams carr;ving much less sulfite liqt: t n:ln in lic :l ted by trF) above rj ilutions. The se obs orv;'..tions su~gest ths.t the aro cumuhtive effects from prolongo :~ exposures to. even v e ry s~iill quantit'i of sulfi t o liquors. Recent expe riments ho. ve .confinled this conclusion, as s ·:ri ous chronic e ffe cts on v fl. ri ous inte rna l orgo.ns of fish have been found . foll owbg long exposur,3S to low conc imtr'.ti ons of sulfite liquor. Al thougr. no ma ~in[),l :~on-h'J.rmful concentra tion for sulfite liquor can be stated rlefi­nite ly at t~, is tir::e ,lilutions as high a s 1:100,000 'l re !mown to have pro­Jucci lcfin ite 18.rr.age to warm water fish.

Sulfnt e '.vnste.--Bl a ck liquor or sulf 'l te waste is uS'.lally quite alkalin unJ if pour e t into str 8(;\.ms in quecntitios large enough to raise the alkalini

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of the water·to pH 8.7 or abave, has !l'lefi:1ite hylrox~rl effect. This waste is lethal only b. strong co~centr<:tiC'nc (Li ",br~:'1m:, 1941). T:10 alkaline substances in the sulfs te wastes. howevGr. act synerGically, particularly inlamacing the Gills ar,i oth E:. r strl.lctur'as secretin g or coverei with mucous, with other toxic :J,gonts in this liquor cv~n : .. t hydroxyl concontrc.tions which are or linarily tol ·J nte i by fish. As Q

result, in.iuries produced by exposure to vcry1ilute black liquor T':a.y lea1 later to the death of the fish fr·oIT'. other causes vmich can strik"j through the w01.\kone J or damage'l pa rt.

Comparatively, tha sulfatQ liquor is more toxic in its ir"t:1e::il;\ t e effects than the sulfite liquor (Vallir:, 1935). In the Fish an:l. ·.hl U ife Service laboratories, concentrations of the sulfe.t·J liquor of 1: 50C) to 1:1,000 are lethal for so:ne WRrE w'3.ter fish in less thf',n 10 2ays even when proper provision is maJ .. e to IT,e.int3.in a suitab le aDount of~issol ve i oxygen. Both fi·3l rl ani labor i:?tory work sho',;v th9.t crJntinuerJ exposur r) to small quanti ties of sulf"'..te liquor pro-lucd s cumulnti V'J eff :: cts in fish and v3.rious foo't org:: .. nisms. Ag<1.in it is im'J')ssible !It this ti:ne to stnt":! definitely the i'1~~imal r .. on-h'H:!'1';ful c')ncentr·-:..t ion of t!-iis waste but inter!",,,,l systemic .:10 rangem~mt s :1f.tV3 b :, cn obs':; rve 1 in fish expose:: to 1: 100 , 00·) :li­Iution of sulfate liquor ~ni it seems pr oh~bl e th~t even sm~ll p r qunntiti~s

of slllf ~lte liquor may h".VG s ·2yi·JUS effeots on fish Iii':) throue;h cur:m l .r.l.t ive aotion.

So .La pulp waste. --So':l.8. pulp v-m ate 'lS f8.r as testa:] 8'-'0:'1S ':l.8'J1Jt :'l,~l_

way b e t 1:'!een sulfat"3 r.:.ni sulfite wastos -:'n ir-,me:ir-·ta toxicity, i:' thc7.c'': ss alkali be neutralize 1. S'lffipl e s of th~s an·s.l~n . W'1.ste stl.l.lia 1 hav·J ~ f!, r!"i'')<l

less volatile toxic mate rial than 3i t 110 r of th0 other t'ilo ch0IT,ical pulp wastas . At pr'~sent little can be So.i ' l c0nc e rni" ~;; the oumul"t ive Soet i on of so .lo. pulp waste, but str2~r:: s which ;nvs r -:: ceiv6.1 .~ VGn SIT'lll qU~lntiti ', s :) f this effluent have shmvn the s am<:i.lo crG c',S0 in f~un ,'.. an::l pro:ucti vi t:v ell': r­act eristio of stroar.:s ,?ollut·-:;:l 'vi th the ')the r chcffiic~, l :::'ulp wCJ.ste s. For­tu..."lately little so'lo. liquor is lost.

Accessory substsncG s. --T',\I'o othor ,?ollut ion hD. zc"r:s ;'1ust be n'ctel 1ee::1.US0 they s"();';~etimes-' complic1.t'3 tho int'Jr?r8t:, ti::.-on of the d~!lg<.:) rs :'J f ~)Ulp mill effluents. K(iny pulp pLlnts blest ,~h thAir pulps, ~n j fr 0C ch10rin8 toge the r;!{ith v:lrious chlorinG blc'lcl':ir.g pO'.\I"}crs n~::..y b G f ::mn l i:"l t~e s fflu­er.ts from those nUls. Fr6e chl orine is hi;hIy t oxic t .:) fish, 1 o.r . ~: . ::.r less being lethal f or many wC.rm water fish, fl. '1 ·.~ !"!"iueh l ow.:; r c 8!:c0ntr r,ti on s Ilre :~te tri!"len t;j,l to 'J'ar:"ous f oo ': o rg~nisms. 1::-1 ~~.: , i ti ')!l chl::Jri" ,,· no.y f orrr: chloraminlJ in the pres8nco of cc rt8.in (u;]lTlcni:': ca l CY'1[.l'JU!'l':S, l,~hich is ,="vc:n more toxic, 90S 0.06 p.::,.r:I. of chlor9.miil-3 C,1n kill trl)ut '-In ~ 0.4 p.:,.:n. warm water fish.

Some mills J:l,:tTIuf" .. cture both pulp '))'1'1 p'lp·~,r, ~tr:·l th'3 ;:ul~ iz tTEJat'3d eith€r before or f\fh]r c<:1.len :t"ring with v r ri olls fill·ers. sizi:!ss, e"~t­ings, an~ even dyes. },:an:v of these subst8.l1ces ,:..re hiGhly t 'Jxic ts f:'sh, an :i as the '''f:lste w8.t;; rs fron such ?:'~r,ts :.:ay carr7 an~T ; J!"' n11 ~f these

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pulp-processing mf-l.terials the effluents from pulp mills ",vhich also manu­facture pap s r often pr8sent pollution problems quite Jifferent from those ~ c scribed f or pulp wastes aL)ne.

Odors

It is well known that wA.stes from paper mills have chn.racteristic unpleo.sant d.ors. In fact, J8rnafe'lt (1936) working with the effects of Vio.st,; w~_ t8 rs fran cellulose plants on plankton ani salmonfoun·-J that there was::' tc.ste in the flesh of the fish ,)xposej to the viaste, whi.ch he attrib ut€-S t') turoentine natorial from the wasta w?te !"s.Furthermore, when the pr .' ~ucts from pape r mills gathe r, stagnate, ~ni riis·i:o.tegrate along the, bot tom below the paner n:ill, the fishes c (lught in these areas often have a taste simi l.·-lr to the cior of the paper mill.

SUIvJ]/ARY

The hun.r:'s to fish fUld other :1quatic life from pulp mill effluents ~:",y be brie fly surr':-:l·l.r ize :~ ~s fo~_ lows:

(1) Lo~se fiber p ollllti ·)n, pro ·-tucins Tr!'lts OIl the bottom of tl)e strc:).m o.n-l on subm9rgel oojocts, with resul t"lnt'lestruction of fish, f :y' ~ en.l s p?wnin!~ groun .'.s, rm-l:~ r8c t 'lmnc-se t o t~ 'J fish themselves.

(2) I!'lr--:·3,~i3.te toxic ..; ff,~cts pr.:; -luc8 ·i by th·) VlD0': .\?xtr.activGs, !. ; . :3irt ~' Gt il ting subst3.nce s A.n ·'t ch0mic')lwfl ste pro-tucts c ont"1.ir.c 'l in

V :c, S~' OL t liquor from tho iigesters ar.d ir, the vTe.sh wret ·a rs.

(.3) ?·:.;luction of~issol von. ;)xycen b thf'l stre<',;1, ','.,f:1 tor beC'1US9

'f the oXYbon:'3m9.~1:.1 s .')f v .'1_ri cus crzanic .:ubst8_r.ces in thesG p'.llp w2s tes.

(4) Cu~ula ti VQ toxic offects. 8 ~/en in Y':;ry hi ,-;hU luti :)ns of t~~ S8 w~stes. 1ue t o th0 spocific t ox ic '1cti on of several orGanic subst::mc8s proJucel or libGrc.t.e'l by tho chemical ,:igestion of the VlOO :'t.

(f,) Spi-:cific tc,y.ic D.c ti on o f v" .rL:·us [! cce s 8ry substctll ce s us e.:'! in t}-ll~ r:J::.).rl·.1f·~cture ·l.nJ proc'3ssing C' f !Ceper an::1 :::,ther p~lp prolucts.

(f ) 11 .. '11 unpL :; so.nt t::l.8te of ton f CU!1 :1 in the fl -3 sh of fish caught in n 5 t~gn~nt area bel ow the paper mill.

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LITERATURE CI TED

JARNEFELT t H. 1936. The effect of waste waters of cellulose f~ctories on the

wo.t'Jr ani the organisms in the Wl.loksi Ri v',)!". Suomen Kc ­misti1ehti 9A t 96-100.

LIEBEANN, H, 1941. Effect of waste water from cellu1ose -man\lfacturing in :lustries

on fish. Agnew Chern. 54, 499- 500.

SUTERriEI STER, E. 1941. Chemistr:r ,)f the pulp B.n'] papur making. 529 pp. New York.

TECHNICAL ASSOCL\.TION OF THE PULP ,\ND PAPE;R INDUSTRY 1943. Technical Association Papers, 26th Se ries, 720 pp. Te~hnica1

Associ ,,, ti on of t he Pulp dn:l P C'.p l?- r In:lustry. New York

VALLIN, STE['! . 1935. Me-ld. strr t en s Un ~'J rs okn. -P·') rs 0k s anst. Sotvattensfisket, K;;1.

Lantbruks-styrels3n . No.5, 39 pp. Chern. Zentr. 1938 11.3438.

1939. 'TlJater pJllution fron: sulf:)t0 cellul o se pbnts. Svrm sk Po.p­perstilu. 42 :251-2.t:)6.

~rrrTlli\~ I! , G. S.

5706

1942. MojA rn pulp an i pape r m~king, ~ crGct ical trea tis e . 705 pp • .R.i~ inhcl 1 Publishing Corpc.pticn., N c'/! Y:.' r~.

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